US5352494A - Process for the production of a composite material protected against oxidation and material obtained by this process - Google Patents

Process for the production of a composite material protected against oxidation and material obtained by this process Download PDF

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US5352494A
US5352494A US07/911,335 US91133592A US5352494A US 5352494 A US5352494 A US 5352494A US 91133592 A US91133592 A US 91133592A US 5352494 A US5352494 A US 5352494A
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layer
carbon
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deposition
aln
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Gerard Rousseau
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Airbus Group SAS
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions

Definitions

  • the present invention relates to a process for the production of a composite material made unoxidizable at high temperature (up to 1800° C. under a low air pressure), as well as to the material obtained by this process.
  • This material is more particularly intended for use as a high performance heat protection for space vehicles (shuttles or aircraft) having to withstand the heating caused by the friction of the air when they reenter the earth's atmosphere at high speed.
  • the invention is also applicable to other industrial fields requiring the use of structures able to withstand high mechanical stresses under temperatures above 1100° C. in a corrosive medium.
  • the oxidation-protected materials to which the invention applies are composite materials, particularly of the carbon-carbon (C/C) type appropriately constituted by carbon fibers embedded in a carbon-based matrix.
  • carbon-carbon materials retain their integrity up to 3000° C. or higher, under rapid heating.
  • their major disadvantage is that they significantly oxidize as from 400° C. in the presence of air.
  • SiC silicon carbide
  • the Applicant has envisaged depositing on the silicon carbide layer an outer oxide layer chosen from among ThO 2 , ZrO 2 , HfO 2 , La 2 O 3 , Y 2 O 3 and Al 2 O 3 and an intermediate layer serving as a reaction barrier between the SiC and the oxide, said intermediate layer being chosen from in particular aluminum nitride and hafnium nitride.
  • the invention therefore relates to a process for producing an oxidation-protected composite material having no silicon carbide coating, as well as to the materials obtained by this process.
  • the invention therefore relates to a process for the production of a material having a composite body which, by an outer coating, is protected against oxidation due to the environment, said body having a substrate of inorganic fibers embedded in a carbon-based matrix, characterized in that it consists of directly depositing on said body an aluminum nitride layer and then on said aluminum nitride layer an outer tight layer of refractory oxide in order to form said outer covering.
  • the outer covering protects the composite material on which it is deposited against the external environment, which is in particular an oxidizing atmosphere such as air.
  • the AlN layer it is desirable for the AlN layer to be as tight as possible and is in crystalline form.
  • the essential function of the AlN layer is as a reaction barrier between the refractory oxide and the carbon of the composite body.
  • AlN aluminum nitride
  • the aluminum nitride (AlN) layer can be deposited by different methods of varying efficiency giving layers which are cracked to a greater or lesser extent as a function of the deposition temperatures used. This phenomenon of the cracking of outer coverings is due to differences in the expansion coefficient between the materials involved.
  • AlN has an expansion coefficient of 4.5 to 5 ⁇ 10 -6 /°C., carbon an expansion coefficient of 1 to 2.5 ⁇ 10 -6 /°C. and graphite an expansion coefficient of 3 to 6 ⁇ 10 -6 /°C.
  • the deposition methods used for the AlN layer are those for which the temperature Tf can be chosen.
  • these methods are essentially chemical vapour phase deposition (CVD) and plasma assisted chemical vapour phase deposition (PECVD).
  • PECVD is used between ambient temperature and 800° C. and CVD between 600° and 1400° C.
  • One or other of these methods can be chosen, as a function of the particular envisaged use of the material.
  • PECVD AlN deposition is carried out with a precursor aluminum chloride (AlCl 3 ) and ammonia (NH 3 ) mixture and also optionally nitrogen, whereas CVD deposition is carried out with a mixture of AlCl 3 and NH 3 , to which hydrogen may be added.
  • AlCl 3 precursor aluminum chloride
  • NH 3 ammonia
  • CVD deposition is carried out with a mixture of AlCl 3 and NH 3 , to which hydrogen may be added.
  • PVD physical vapour phase deposition
  • Nitriding firstly consists of depositing an aluminum layer by cathodic sputtering or evaporation on the composite body and then placing the entity in a nitriding furnace, where progressive heating takes place under a nitrogen atmosphere. Nitriding starts at about 600° C. and the material is progressively heated to 1200° C., which is the temperature where the complete consolidation of the nitride layer takes place.
  • the AlN layers obtained have a thickness of 1 to 5 micrometers.
  • Reactive PVD methods give rise to low temperature (20° to 600° C.), very thin (approximately 1 to 5 micrometer) layers. Therefore these methods can only be used for materials to be employed at low temperatures, so as to limit the formation of cracks by compression during their use.
  • This surface alumina is slightly porous and then slows down the penetration of the oxygen into the AlN layer.
  • This natural layer of Al 2 O 3 favors the protection against oxidation of the composite material, in view of the fact that alumina is a material able to withstand heat and oxidation.
  • the aluminum nitride reacts with the carbon in the composite material in order to form an interface aluminum carbide (Al 4 C 3 ) layer, which assists the attachment of AlN to the material, thus ensuring a good adhesion of said AlN layer to the carbon.
  • the material is heated at between 600° and 1000° C., in order to ensure the formation of said interface layer.
  • This heating stage can be arbitrary or can result from the subsequent deposition of a high temperature protection layer (>600° C.).
  • the thickness of the interface layer increases to a limit value of approximately 1 micrometer.
  • PECVD or CVD deposition methods are preferred, because they make it possible to deposit a layer of desired thickness. In particular, these methods make it possible to deposit a 10 to 100 micrometer thick AlN layer. The precise thickness of the AlN layer is a function of its use.
  • the outer oxide layer has the function of preventing at high temperature and in particular under reduced pressure (1800° C. under 2.8 kPa or 2000° C. under 20 kPa), the penetration of oxygen from the environment (generally air) into the composite material. Therefore said layer must have a low gas permeability and good refractory characteristics. In particular, said layer must be crystalline and non-porous.
  • alumina Preference is given to the use of alumina as a result of its lower oxygen diffusion coefficient.
  • the diffusion coefficient of oxygen in alumina at 1200° C. is 3.10 -16 cm 2 /s, i.e. 100 times lower than that of silica, which is 3.10 -14 cm 2 /s.
  • Its expansion coefficient is 8 to 9 ⁇ 10 -6 /°C.
  • the deposited alumina is alpha-alumina.
  • the refractory oxide layer deposition methods are in particular PECVD or CVD.
  • the PECVD deposition temperature is between 200° and 800° C., whereas in the case of CVD method they are between 800° and 1400° C.
  • the precursor gases for PECVD alumina deposition are aluminum chloride, oxygen and hydrogen.
  • the deposition of an alumina layer takes place by gas phase hydrolysis of aluminum chloride.
  • the hydrolysis water is formed in situ in the reactor by the reaction of carbon dioxide gas on hydrogen. The following reactions are involved:
  • the reaction is essentially governed by the production of the water responsible for the hydrolysis of the aluminum chloride. Deposition takes place with a ratio of the partial hydrogen and carbon dioxide gas pressures close to 1.
  • the partial pressure of the aluminum chloride is relatively low and in particular below 0.5 kPa, so as to assist during deposition the diffusion of reactive species with respect to the formation kinetics of the alumina on the surface.
  • the temperature of the carbon-containing material must not be too high, preferably below 1100° C.
  • the deposition speed is solely controlled by the chemical reaction rate on the surface of the material.
  • the thickness of the oxide layer obtained by PECVD or CVD is between 3 and 100 micrometers, as a function of the use conditions intended for the carbon-containing material.
  • the cracks existing in the underlying AlN covering re-form. They are then resealed during the use of the composite material as soon as the temperature reaches the alumina deposition temperature of in this case 1000° C.
  • the cracks in the refractory oxide layer reseal during the use of the material as soon as the use temperature exceeds the oxide deposition temperature (particularly 1000° C.).
  • CVD or PECVD methods for the deposition of the oxide layer
  • PVD physical vapour phase deposition
  • Plasma spraying gives relatively thick coverings ( ⁇ 100 micrometers), but unfortunately they are not very tightly sealed, whilst PVD methods give relatively thin coverings of 1 to 10 micrometers.
  • This layer can be formed by CVD or PECVD under the same operating conditions as for AlN by adding to the mixture reactive gases such as oxygen or CO 2 .
  • the process according to the invention is applicable to all types of composite material constituted by a fibrous substrate (carbon, graphite, ceramic, SiC, BN, Al 2 O 3 , etc.) embedded in a carbon-based matrix (graphitic, pyrolytic or vitreous carbon).
  • a fibrous substrate carbon, graphite, ceramic, SiC, BN, Al 2 O 3 , etc.
  • carbon-based matrix graphitic, pyrolytic or vitreous carbon
  • said matrix can be optionally doped by silicon carbide, boron nitride or carbide, i.e. contains less than 20% and in particular 2 to 10% by weight SiC, B 4 C or BN.
  • SiC-containing matrix The production of a SiC-containing matrix is described in FR-A-2 611 198. It more particularly consists of impregnating the fibrous substrate in vacuo by a phenolic resin of the resol type on which 10% of the silicone functions (SiO) have been chemically grafted, followed by hot polymerization and high temperature pyrolysis (approximately 800° C.) of the resin.
  • the carbon matrix is obtained in known manner by the pyrolysis of a thermosetting resin with a high carbon content, such as phenolic resins, by cracking hydrocarbons such as methane, propane, ethane or butane or by the pyrolysis of a coal tar at about 800° C.
  • a thermosetting resin with a high carbon content such as phenolic resins
  • hydrocarbons such as methane, propane, ethane or butane
  • each fiber of the substrate is covered with a thin silicon carbide layer with a thickness of 100 to 200 nm, in order to preserve the deformability of the substrate for its shaping during the production of a particular part, prior to forming the matrix by densification.
  • This SiC layer on the fibers is deposited by CVD using a gaseous mixture containing one or more organosilanes, which may or may not be substituted by a halogen optionally associated with one or more gaseous hydrocarbons and/or hydrogen.
  • the organosilanes which can be used are in particular chlorosilanes of form (CH 3 ) n SiCl.sub.(4-n) with 0 ⁇ n ⁇ 4.
  • the hydrocarbons are in particular methane, ethane, propane and butane.
  • use is made of a mixture of trichloromethyl silane and hydrogen with a ratio (H 2 )/(CH 3 SiCl 3 ) 4 to 12.
  • silicon carbide on the surface of the substrate fibers and in the matrix makes it possible to ensure an anti-oxidation protection which greatly slows down the core oxidation of the composite carbon-carbon material in the case of an accidental destruction of the AlN layer.
  • the surface of each fiber can be provided with a pyrolytic carbon layer in contact with the SiC film coating these fibers.
  • This pyrolytic carbon layer can be deposited prior to the SiC film of the fibers or afterwards.
  • This pyrolytic carbon layer constitutes an interface which preserves, or even improves, the mechanical properties of the composite material.
  • This pyrolytic carbon layer is deposited by high temperature CVD using one of the aforementioned hydrocarbons.
  • the invention also relates to a material obtained by the process described hereinbefore.
  • the invention relates to a material incorporating a composite body protected by an outer covering against environmental oxidation, said body incorporating a substrate of mineral fibers embedded in a carbon-based matrix, characterized in that the outer covering has an interface aluminum carbide layer in direct contact with the composite body, an aluminum nitride layer in direct contact with the interface layer and a tight refractory oxide outer layer covering the aluminum nitride layer.
  • FIGS. 1, 2, 3 and 4 diagramatically showing in cross-section different embodiments of the carbon-containing material protected against oxidation in accordance with the present invention.
  • the material shown in FIG. 1 has a pyrolytic carbon body 2 obtained in per se known manner by pyrolysis in an appropriately shaped mould of a thermosetting resin having a high carbon content. Directly on the surface of the material is deposited by PECVD at above 600° C. of an aluminum nitride layer 4. This deposition takes place in a vacuum of 50 Pa. The deposition speed is a few micrometres per hour.
  • the AlN layer 4 is 10 to 100 micrometers thick. It is tight and crystallized in hexagonal form.
  • the relative quantities of each gas are defined by the following ratios:
  • This AlN deposition takes place at a temperature above 600° C., the AlN reacting with the carbon of the support 2 in order to form an aluminum carbide (Al 4 C 3 ) layer 6.
  • this is followed by the deposition on the AlN layer 4 of a tight alpha alumina layer 8 with a thickness of 3 to 100 micrometres at 500° C. and using PECVD.
  • the pressure in the deposition enclosure is relatively low and in particular below 50 Pa.
  • This alumina deposition is obtained with a gaseous mixture defined by the ratios:
  • the thus obtained material is free from cracks, both with regards to the AlN layer and the alumina layer and can be used up to approximately 1300° C. in an atmosphere containing or not containing oxygen of 10 to 10 5 Pa.
  • the alumina covering scales off at above 1300° C.
  • FIG. 2 shows the composite carbon-carbon material with graphite or carbon reinforcing fibers 12 embedded in a graphitic carbon matrix 14. These fibers 12 are woven or wound in two or three directions and have an approximate thickness of 8 micrometers. They can be short or long with a high resistance or a high modulus.
  • Each fiber 12 is coated by an extremely thin, 100 to 150 nm thick, pyrolytic carbon, anisotropic film 16.
  • the latter is obtained by CVD at 1100° C. in furnace, where methane circulates under a pressure of 1.5 kPa.
  • silicon carbide layer 18 protects each fiber 12 from a possible core oxidation, by slowing down the diffusion of the oxygen.
  • the outer surface of the matrix 14 is covered by a tight AlN layer 4 deposited by PECVD at 600° C. and then a tight alumina layer 8 deposited by PECVD at 500° C.
  • the AlN and alumina deposition conditions are identical to those described relative to FIG. 1. However, as the AlN deposition temperature is at the most equal to 600° C., a managed heating to a temperature above 1000° C. is carried out in order to form the Al 4 C 3 attachment layer 6.
  • This material has no cracks and can be used up to 1000° C. in an oxygen atmosphere.
  • FIG. 3 shows another material according to the invention.
  • the aluminum nitride layer is deposited by CVD at between 600° and 1000° C. and in particular at 950° C. in an isothermal furnace, where circulation takes place under a reduced pressure of 500 to 1000 Pa of ammonia, hydrogen and aluminium chloride, accompanied by the scavenging of a neutral gas such as helium or argon.
  • CVD leads to the formation of cracks 20 in the AlN layer 4, as well as cracks 22 in the underlying aluminum carbide layer 6 and these constitute sources for the penetration of oxygen at below the production temperature. This leads to the natural formation of a slightly porous alumina layer 24 on the surface of the AlN layer and in the cracks 20 thereof, which slows down oxygen penetration.
  • the outermost layer of the material is a tight alpha alumina layer 8 deposited by CVD at 600° to 1000° C. and in particular at 1000° C. This alumina deposition takes place under a reduced pressure of 5 kPa with a mixture of gases containing by volume 1% AlCl 3 , 49.5% H 2 O and 49.5% CO 2 .
  • This example corresponds to a general case with a high use temperature of approximately 2000° C. for an air pressure of approximately 1 to 100 kPa.
  • the material example shown in FIG. 4 differs from the previous embodiments by the deposition of an AlN layer 4 by PECVD at 400° C., under the same conditions as described with reference to FIG. 1, followed by a tight alumina deposit 8 using CVD at 950° C. It also differs through the absence of a pyrolytic carbon layer and a SiC carbide layer on the fibers 12.
  • the alumina layer deposition temperature which exceeds 600° C., leads to the formation of the aluminum carbide interface layer 6.
  • alumina by CVD leads to the formation of cracks 26 on its surface, which can bring about a slight penetration of oxygen into the alumina layer and thus create on its surface a natural alumina layer 24.
  • the example shown in FIG. 4 corresponds to a use temperature up to 1300° C. for a carbon matrix.
  • the use temperature extends to 1300° C.

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US07/911,335 1989-11-09 1992-07-08 Process for the production of a composite material protected against oxidation and material obtained by this process Expired - Fee Related US5352494A (en)

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FR8914703A FR2654094B1 (fr) 1989-11-09 1989-11-09 Procede de fabrication d'un materiau carbone protege contre l'oxydation par du nitrure d'aluminium et materiau obtenu par ce procede.
FR8914703 1989-11-09
US60565690A 1990-10-10 1990-10-10
US07/911,335 US5352494A (en) 1989-11-09 1992-07-08 Process for the production of a composite material protected against oxidation and material obtained by this process

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US (1) US5352494A (fr)
EP (1) EP0427629B1 (fr)
JP (1) JPH03187989A (fr)
AT (1) ATE118469T1 (fr)
CA (1) CA2029382A1 (fr)
DE (1) DE69016930T2 (fr)
FR (1) FR2654094B1 (fr)
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Cited By (13)

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US5674564A (en) * 1991-06-25 1997-10-07 Sandvik Ab Alumina-coated sintered body
US6180189B1 (en) * 1997-04-26 2001-01-30 Daimlerchrysler Ag Method and apparatus for aluminum nitride coating of a contact surface, especially a cylinder contact surface of a crankcase made of an aluminum basic alloy
US20050208718A1 (en) * 2004-03-16 2005-09-22 Lim Jae-Soon Methods of forming a capacitor using an atomic layer deposition process
US20050276990A1 (en) * 2002-08-08 2005-12-15 Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd) Process for producing alumina coating composed mainly of alpha-type crystal structure, alumina coating composed mainly of alpha-type crystal structure, laminate coating including the alumina coating, member clad with the alumina coating or laminate coating, process for producing the member, and physical evaporation apparatu
US20090197075A1 (en) * 2008-02-01 2009-08-06 United Technologies Corporation Coatings and coating processes for molybdenum substrates
US11046619B2 (en) 2018-08-13 2021-06-29 Goodrich Corporation High temperature oxidation protection for composites
US11091402B2 (en) 2016-12-15 2021-08-17 Goodrich Coporation High temperature oxidation protection for composites
US11168222B2 (en) 2016-06-27 2021-11-09 Goodrich Corporation High temperature oxidation protection for composites
US11325868B2 (en) 2016-05-31 2022-05-10 Goodrich Corporation High temperature oxidation protection for composites
EP4086234A1 (fr) * 2021-05-05 2022-11-09 Goodrich Corporation Protection contre l'oxydation à haute température pour des composites carbone-carbone
US11634213B2 (en) 2018-11-14 2023-04-25 Goodrich Corporation High temperature oxidation protection for composites
EP4180408A1 (fr) * 2021-11-16 2023-05-17 Goodrich Corporation Protection contre l'oxydation à haute température pour composites carbone-carbone
US11877687B2 (en) * 2015-07-27 2024-01-23 The United States Of America As Represented By The Secretary Of The Army Heater and cookware for flameless catalytic combustion

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FR2686336B1 (fr) * 1992-01-20 1995-01-13 Aerospatiale Piece en materiau composite carbone-carbone a matrice dopee sic, resistant a l'oxydation et son procede de fabrication.
FR2737702B1 (fr) * 1995-08-10 1997-09-26 Oreal Dispositif de conditionnement et de distribution
DE10009432C1 (de) 2000-02-28 2001-12-06 Mtu Aero Engines Gmbh Bürste für eine Bürstendichtung
FR2909998B1 (fr) * 2006-12-18 2009-03-06 Snecma Propulsion Solide Sa Piece en materiau composite a matrice ceramique contenant du silicium, protegee contre la corrosion

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US20050276990A1 (en) * 2002-08-08 2005-12-15 Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd) Process for producing alumina coating composed mainly of alpha-type crystal structure, alumina coating composed mainly of alpha-type crystal structure, laminate coating including the alumina coating, member clad with the alumina coating or laminate coating, process for producing the member, and physical evaporation apparatu
US7531212B2 (en) * 2002-08-08 2009-05-12 Kobe Steel, Ltd. Process for producing an alumina coating comprised mainly of α crystal structure
US20050208718A1 (en) * 2004-03-16 2005-09-22 Lim Jae-Soon Methods of forming a capacitor using an atomic layer deposition process
US7361548B2 (en) * 2004-03-16 2008-04-22 Samsung Electronics Co., Ltd. Methods of forming a capacitor using an atomic layer deposition process
US20090197075A1 (en) * 2008-02-01 2009-08-06 United Technologies Corporation Coatings and coating processes for molybdenum substrates
US11877687B2 (en) * 2015-07-27 2024-01-23 The United States Of America As Represented By The Secretary Of The Army Heater and cookware for flameless catalytic combustion
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US20230150884A1 (en) * 2021-11-16 2023-05-18 Goodrich Corporation High temperature oxidation protection for carbon-carbon composites

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IE70915B1 (en) 1997-01-15
ATE118469T1 (de) 1995-03-15
FR2654094B1 (fr) 1993-07-09
DE69016930D1 (de) 1995-03-23
EP0427629B1 (fr) 1995-02-15
CA2029382A1 (fr) 1991-05-10
DE69016930T2 (de) 1995-09-07
IE903915A1 (en) 1991-05-22
FR2654094A1 (fr) 1991-05-10
NO904840D0 (no) 1990-11-07
JPH03187989A (ja) 1991-08-15
NO904840L (no) 1991-05-10
EP0427629A1 (fr) 1991-05-15

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